CA1263955A - Coating materials stabilised against the action of light - Google Patents
Coating materials stabilised against the action of lightInfo
- Publication number
- CA1263955A CA1263955A CA000494241A CA494241A CA1263955A CA 1263955 A CA1263955 A CA 1263955A CA 000494241 A CA000494241 A CA 000494241A CA 494241 A CA494241 A CA 494241A CA 1263955 A CA1263955 A CA 1263955A
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- Prior art keywords
- alkyl
- formula
- group
- phenyl
- hydrogen
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
Abstract
Case 3-15131/1-3 Coating materials stabilised against the action of light Abstract Blocked benzotriazoles of the formula I or II
I
II
wherein x is 1 or 2, R1 in the case of x=1 and in the formula II is an acyl group of the formula -CO-R5, a sulfonyl group of the formula -SO2-R6, a phosphoryl group of the formula -P(O)r(R14)(R15), and in the case of x=2 is -CO- or a diacyl group of the formula -CO-CO- or -CO-R7-CO-, and R2, R3, R4, R5, R6, R7, R14 and R15 have the meanings defined in claim 1, are crypto light stabilisers which can be activated by short-wave irradiation. Their use in coating materials is of interest in cases in which light stabilisers containing the free OH compounds have disadvantages with regard to their application.
I
II
wherein x is 1 or 2, R1 in the case of x=1 and in the formula II is an acyl group of the formula -CO-R5, a sulfonyl group of the formula -SO2-R6, a phosphoryl group of the formula -P(O)r(R14)(R15), and in the case of x=2 is -CO- or a diacyl group of the formula -CO-CO- or -CO-R7-CO-, and R2, R3, R4, R5, R6, R7, R14 and R15 have the meanings defined in claim 1, are crypto light stabilisers which can be activated by short-wave irradiation. Their use in coating materials is of interest in cases in which light stabilisers containing the free OH compounds have disadvantages with regard to their application.
Description
~ ~3~`35~
Case 3-15131/1-3 Coatin~ materials stabilised against th_ action of li~ht The invention relates to coating materials containing cryp~o light stabilisers. Such compounds are activated by the action of short-wave light in that they are converted photochemically lnto light stabilisers. The compounds concerned are specific derivatives of 2-(2-hydroxyphenyl)-benzotriazoles having a blocked hydroxyl group.
Olson and Schroeter (J. Appl. Pol. Science 22 (1978), 2165-72) have already suggested blocking the phenolic hydroxyl group of 2-(2-hydroxyphenyl)-benzotriazoles with chemical protective groups which are subsequently removable, for example by hydrolysis, photolysis or heating. These blocked benzotriazole derivatives do not absorb in the W range o 330 - 400 nm and as a result do not disturb the photopolymerisation of W -curable compositions.
Because of their changed W -absorption level ~their absorption maximum is about 290 - 310 nm), they are however not suitable as light stabilisers, and have therefor~e to be converted after photopolymerisation into the benzotriazoles having a free OH group,~which are known light stabilisers. The stated authors investigated the possibility of blocking the OH group by silylation, by carbamoylation and, in a ... .
i3~s3~5 later work (J. Appl. Pol. Science 28 (198~), 1159 - 65), also by etherification, esterifica~ion ancl sulfonylation.
Various problems arise in this connection, such as insufficient cleavage or discoloration resulting from the formation of by-products. The O-sulfonylation and photochemical cleavage are described as being the best methods. In the case of this cleavage, there occurs essentially a photochemical Fries rearrangement to the ortho-sulfonylphenols. This is possible because all examined compounds are unsubstituted in the ortho-position (with respect to the OH group).
It has now been found that with the use of 2-(2-hydroxy-phenyl)-benzotriazoles, which are substltuted both in the para-position and ~n the ortho-position with respect to the OH group, there are obtained, by blocking o~ the OH group, cryp~o light stabilisers which have an absorption maximum likewise at 290 - 310 nm but which, in spite of the substitution in the para-position and in the ortho-position, can be photochemically reconverted i~to co~pounds having a free OH group. They have a level of stability in darkness which is higher than that of the compounds having an unsubstituted ortho-position. This factor is important with respect to the commercial application, since lacquers are frequently stored for long periads.
Compared with the known benzotriazole light stabilisers having a free OH group, these crypto light stabilisers are of advantage when the co~ting material is in contact with metals before or during application. All 2-(2-hydroxyphenyl)-benzotriazoles form with metal ions complexes which are often coloured (for example in the case of Cu, Ni or Co), and they can then cause a discoloration of the coa~ing material. Another interesting field of ~ 5t~
application for crypto ligh~ stabilisers is that covering oxidatively drying coating materials which contain, as curing catalysts (siccatives)~ organic metal compounds.
In the presence of free 2-(2-hydroxyphenyl)-benzotriazoles, these metal compounds are bound by coordination to the benzotriazole, and are then no longer effective as curing catalysts.
The present invention thus relates to coating materials containing, as a crypto light stabiliser, a compound of the formula I or II
- ! Rl _ x , _ wherein x is 1 or 2, Rl in the case of x=l and in che formula II is an acyl group of the formula Co-R5, a sulfonyl group of thé
formula -S02-R6, a phosphoryl group of the formula ~P(O)r(R 4)(R 5), and in the case of x=2 is -CO- or a diacyl group of the formula -CO-CO- or -Co-R7-Co-, ~ ~ ~3 ~J~;
s Cl C12 alkyl~ Cs-C12-cycloalkyl, phenyl, C -C -phenylalkyl, C3-C5-alkenyl or halogen, R in the formula I is Cl-C12-alkyl, C5-C12-cycloalkyl, phenyl, C7-C9-phenylalkyl, halogen or a group of the formula -(CH2)n-CooR9 or -(CH2)n-CO-N(R O)(Rll), and in the formula II is a divalent radical o~ the formula:
~(CH2)n~CO~O~(CH2)q~0~CO~(CH2)n~, -(CH2~n-CO-O-(CH2CH20)p-CO-(CH2)n~, (CH ) CO NH R12 NH CO (CH ) - or (CH2)n CO CH2 ,CH13CH2 (CH2)q CH2 ,CH13CH2 ( 2)n R4 is hydrogen, halogen, Cl-C8-alkyl, C7-C9-phenylalkyl, Cl-C8-alkoxy or C2-C8-alkoxycarbonyl, R5 is Cl-C18-alkyl, C2-C18-alkenyl, -CH2-CO-CH3, phenyl, phenyl substituted by Cl-C12-alkyl, cl-c4-alkoxy or benzoyl, C7-C12-aryLalkyl or Cl-C12-alkoxy, R is cl-cl2-alkyl, C6-C10 aryl or C7-Cl8-alkylaryl~
R7 is Cl-C10-alkylene or phenylene, R9 is hydrogen, Cl-C12-alkyl or a group of the for~ula -~CH2CH20)p-R , R10 and Rll independently o~ one another are hydr.ogen, Cl-C12-alkyl, which can be interrupted by O or N, C5-C12-cyclo-alkylj C7-C9-phenylalkyl, C3-C5-alkenyl, phenyl or a
Case 3-15131/1-3 Coatin~ materials stabilised against th_ action of li~ht The invention relates to coating materials containing cryp~o light stabilisers. Such compounds are activated by the action of short-wave light in that they are converted photochemically lnto light stabilisers. The compounds concerned are specific derivatives of 2-(2-hydroxyphenyl)-benzotriazoles having a blocked hydroxyl group.
Olson and Schroeter (J. Appl. Pol. Science 22 (1978), 2165-72) have already suggested blocking the phenolic hydroxyl group of 2-(2-hydroxyphenyl)-benzotriazoles with chemical protective groups which are subsequently removable, for example by hydrolysis, photolysis or heating. These blocked benzotriazole derivatives do not absorb in the W range o 330 - 400 nm and as a result do not disturb the photopolymerisation of W -curable compositions.
Because of their changed W -absorption level ~their absorption maximum is about 290 - 310 nm), they are however not suitable as light stabilisers, and have therefor~e to be converted after photopolymerisation into the benzotriazoles having a free OH group,~which are known light stabilisers. The stated authors investigated the possibility of blocking the OH group by silylation, by carbamoylation and, in a ... .
i3~s3~5 later work (J. Appl. Pol. Science 28 (198~), 1159 - 65), also by etherification, esterifica~ion ancl sulfonylation.
Various problems arise in this connection, such as insufficient cleavage or discoloration resulting from the formation of by-products. The O-sulfonylation and photochemical cleavage are described as being the best methods. In the case of this cleavage, there occurs essentially a photochemical Fries rearrangement to the ortho-sulfonylphenols. This is possible because all examined compounds are unsubstituted in the ortho-position (with respect to the OH group).
It has now been found that with the use of 2-(2-hydroxy-phenyl)-benzotriazoles, which are substltuted both in the para-position and ~n the ortho-position with respect to the OH group, there are obtained, by blocking o~ the OH group, cryp~o light stabilisers which have an absorption maximum likewise at 290 - 310 nm but which, in spite of the substitution in the para-position and in the ortho-position, can be photochemically reconverted i~to co~pounds having a free OH group. They have a level of stability in darkness which is higher than that of the compounds having an unsubstituted ortho-position. This factor is important with respect to the commercial application, since lacquers are frequently stored for long periads.
Compared with the known benzotriazole light stabilisers having a free OH group, these crypto light stabilisers are of advantage when the co~ting material is in contact with metals before or during application. All 2-(2-hydroxyphenyl)-benzotriazoles form with metal ions complexes which are often coloured (for example in the case of Cu, Ni or Co), and they can then cause a discoloration of the coa~ing material. Another interesting field of ~ 5t~
application for crypto ligh~ stabilisers is that covering oxidatively drying coating materials which contain, as curing catalysts (siccatives)~ organic metal compounds.
In the presence of free 2-(2-hydroxyphenyl)-benzotriazoles, these metal compounds are bound by coordination to the benzotriazole, and are then no longer effective as curing catalysts.
The present invention thus relates to coating materials containing, as a crypto light stabiliser, a compound of the formula I or II
- ! Rl _ x , _ wherein x is 1 or 2, Rl in the case of x=l and in che formula II is an acyl group of the formula Co-R5, a sulfonyl group of thé
formula -S02-R6, a phosphoryl group of the formula ~P(O)r(R 4)(R 5), and in the case of x=2 is -CO- or a diacyl group of the formula -CO-CO- or -Co-R7-Co-, ~ ~ ~3 ~J~;
s Cl C12 alkyl~ Cs-C12-cycloalkyl, phenyl, C -C -phenylalkyl, C3-C5-alkenyl or halogen, R in the formula I is Cl-C12-alkyl, C5-C12-cycloalkyl, phenyl, C7-C9-phenylalkyl, halogen or a group of the formula -(CH2)n-CooR9 or -(CH2)n-CO-N(R O)(Rll), and in the formula II is a divalent radical o~ the formula:
~(CH2)n~CO~O~(CH2)q~0~CO~(CH2)n~, -(CH2~n-CO-O-(CH2CH20)p-CO-(CH2)n~, (CH ) CO NH R12 NH CO (CH ) - or (CH2)n CO CH2 ,CH13CH2 (CH2)q CH2 ,CH13CH2 ( 2)n R4 is hydrogen, halogen, Cl-C8-alkyl, C7-C9-phenylalkyl, Cl-C8-alkoxy or C2-C8-alkoxycarbonyl, R5 is Cl-C18-alkyl, C2-C18-alkenyl, -CH2-CO-CH3, phenyl, phenyl substituted by Cl-C12-alkyl, cl-c4-alkoxy or benzoyl, C7-C12-aryLalkyl or Cl-C12-alkoxy, R is cl-cl2-alkyl, C6-C10 aryl or C7-Cl8-alkylaryl~
R7 is Cl-C10-alkylene or phenylene, R9 is hydrogen, Cl-C12-alkyl or a group of the for~ula -~CH2CH20)p-R , R10 and Rll independently o~ one another are hydr.ogen, Cl-C12-alkyl, which can be interrupted by O or N, C5-C12-cyclo-alkylj C7-C9-phenylalkyl, C3-C5-alkenyl, phenyl or a
2,2,6,6-tetramethyl-4-piperidinyl radical, or R and R
together are c4-C6-alkylene, -oxaalkylene or -azaalkylene, R12 is Cl-C12-alkylene, which can be interrupted by 1-3 0 atoms,
together are c4-C6-alkylene, -oxaalkylene or -azaalkylene, R12 is Cl-C12-alkylene, which can be interrupted by 1-3 0 atoms,
3 is Cl-C12~alkYl or C6 C10 Y
~ ~3 ~ ~
R and R 5 independently of one another are each Cl-C12-alkoxy, phenoxy, Cl-C12-alkyl, cyclohexyl, benzyl, phenyl or tolyl, n is 1 or 2, p is a number from 1 to 10, q is a num~er ~rom 2 to 12, and r is O or 1.
As a monovalent acyl group, R can be for example:
acetyl, propionyl, butyryl, valerianyl, capronyl (n-hexanoyl), 2-ethylhexanoyl, capryloyl (n-octanoyl), caprionyl (n-decanoyl), lauroyl (n-dodecanoyl), palmityl (n-hexadecanoyl), stearoyl. ~n-octadecanoyl), acryloyl, methacryloyl, crotonyl, oleyl, linoleyl, benzoyl, 3-methyl-benzoyl, ~-tert-butylbenxoyl~ 4-he~ylbenzoyl, ~-dodecyl-benzoyl, 3- or ~-methoxy- or -et~loxybenzoyl, ~-benzoyl-benzoyl, phenylacetyl, phenylpropionyl, naphthylacetyl, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octyloxy-carbonyl or dodecyloxycarbonyl. ExampLes of Rl as a sulfonyl group are the groups: methyl-, tert-butyl-, octyl-, dodecyl-, phenyl-, tolyl-, naph-thyl-, 4-nonylphenyl-,
~ ~3 ~ ~
R and R 5 independently of one another are each Cl-C12-alkoxy, phenoxy, Cl-C12-alkyl, cyclohexyl, benzyl, phenyl or tolyl, n is 1 or 2, p is a number from 1 to 10, q is a num~er ~rom 2 to 12, and r is O or 1.
As a monovalent acyl group, R can be for example:
acetyl, propionyl, butyryl, valerianyl, capronyl (n-hexanoyl), 2-ethylhexanoyl, capryloyl (n-octanoyl), caprionyl (n-decanoyl), lauroyl (n-dodecanoyl), palmityl (n-hexadecanoyl), stearoyl. ~n-octadecanoyl), acryloyl, methacryloyl, crotonyl, oleyl, linoleyl, benzoyl, 3-methyl-benzoyl, ~-tert-butylbenxoyl~ 4-he~ylbenzoyl, ~-dodecyl-benzoyl, 3- or ~-methoxy- or -et~loxybenzoyl, ~-benzoyl-benzoyl, phenylacetyl, phenylpropionyl, naphthylacetyl, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octyloxy-carbonyl or dodecyloxycarbonyl. ExampLes of Rl as a sulfonyl group are the groups: methyl-, tert-butyl-, octyl-, dodecyl-, phenyl-, tolyl-, naph-thyl-, 4-nonylphenyl-,
4-dodecylphenyl- or mesitylenesulfonyl.
R as a diacyl group-can be for example: oxalyl, succinyl, glutaroyl, adipoyl, 2,2,4-trimethyladipoyl, sebacoyl (octamethylenedicarbonyl), decamethylenedicarbonyl, terephthaloyl or isophthaloyl. R , R3, R , R , R , R
R 3, R 4, R 5 as alkyl can, within the given number of C atoms, be for example: methyl, ethyl, propyl, isopropyl, n butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl or dodecyl.
R and R3 are preferably branched-chain alkyl groups.
R10 and Rll as alkyl interrupted by O or N can be for example: 2-butoxyethyl, 3-methoxypropyl, 3-e~hoxy-propyl, 3-isopropoxypropyl, 3-butylaminopropyl or 3-ethyl-aminopropyl.
. . .
~ ~ ~3 ~5 S
R2, R10 and Rll as alkenyl can be for example: allyl, methallyl or 2-butenyl.
R14 and R15 as alkoxy can be ~or example: methoxy, ethoxy, isopropoxy, butoxy, hexyloxy, octyloxy9 decyloxy or dodecyloxy.
R2 and R3 as halogen can be for example: fluorine, chlorine or bromine.
R , R3, R10 and Rll as cycloalkyl can be for example:
cyclopentyl, cyclohexyl, methylcyclohexyl, cyclooctyl or cyclododecyl.
R2, R3, R10 and Rll as phenylalkyl can be for example:
benzyl, a-methylbenzyl, a-dimethylbenzyl or 2-phenylethyl.
R and R as phenylalkyl are preferably a-dimethylbenzyl.
R~ as alkoxy or alkoxycarbonyl can be for example:
methoxy, ethoxy, isopropoxy, butoxy, hexyloxy, octyloxy, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl or pentyl-oxycarbonyl. Cl-C4-alkoxy or alkoxycarbonyl radicals are preferred.
R7 as alkylene can be for example: methylene, 1,2-ethylene, tri-, tetra-, penta-, hexa-, octa- or deca-methylene.
When R10 and Rll together are alkylene, oxa- or aza-alkylene, they form together with the N atom to which they are bound a heterocyclic ring, for example a pyrrolidine, piperidine, morpholine, piperazine or hexamethylene ring.
R12 can be for example: 1,2-ethylene, tri-, tetra-, penta-, hexa-, octa- or dodecamethylene, 2,4,4-trimethyl-hexamethylene, 3-oxaheptamethylene or 3,6-dioxa-decamethylene.
,:
~L2~3~
Preferred compounds of the formula I are those wherein x = 1, Rl is a group of the formula -Co-R5, -S02-R6 or -P(O) (R 4)(R15), R2 is Cl-C12-alkyl, cyclohexyl or C7-Cg-phenylalkyl, R is Cl-Cl~-alkyl, cyclohexyl, C7 Cg-phenylalkyl or a group -CH2CH2COOR , R is hydrogen, methyl or chlorine, R5 is Cl-cl2~alkYl~ C2-C4-alkenYl' phenyl~
benzyl or naph~hylmethyl, R is methyl, phenyl or C7-C18-alkylphenyl, R9 is Cl-C12-alkyl, and R14 and R15 independently of one another are each Cl-C4-alkoxy, methyl or phenyl. Preferably, R therein is a group -CO-R or -S02-R , R is Cl-C8-alkyl or a-dimethylbenzyl, R is Cl-C8-alkyl, a-dimethylbenzyl or a group -CH2CH2COOR , and R4 is hydrogen or chlorine.
Particularly preerrecl compounds of the ormula I are those wherein x=L, Rl is a group -Co~R5 or -S02-R , R2 is Cl-C8-alkyl or a-dimethylbenzyl, R3 is Cl-C8-alkyl, a-dimethylbenzyl or -CH2CH2COOR , R is hydrogen or chlorine, R is Cl-cl2-alkyL~ C2-C4-alkenyl, phenyl, benzyl or naphthylmethyl, R is methyl, phenyl or C7-C18-alkylphenyl, and R9 is cl-C12-alkyl.
Preferred also are compounds of the formula I wherein x=2, R is a group -Co-R7-Co-, R is Cl-C8-alkyl or a-dimethylbenzyl, R is Cl-C8-alkyl, a-dimethylbenzyl or a group -CH2CH2COOR , R is hydrogen or chlorine, R is C2-C8-alkylene, and R is Cl-C12-alkyl.
: Further preferred compounds are those of the formula II
wherein R is a group -CO-R or -S02-R , R is Cl C8-alkyl : or a-dimethylbenzyl, R is a group of the formula .
CH COO (C~ ) -OCOCH2CH2- o5r -CH2CH2C 2 R is hydrogen or chlorine, R is Cl-C12-alkyl, C2-C~-alkenyl, phenyl, benzyl or naphthylmethyl, R is methyl, phenyl or C7-C18-alkylphenyl~ R12 is C2-C8-alkylene, and q is a number from 2 to 8.
~"
~ 2 ~3~ 5 Some of these compounds are known and some are novel compounds. They can be produced essentially from the corresponding hydroxyl compounds (Rl = H) by esterification of the hydroxyl group, using the customary methods of acylation of phenolic OH groups, for example by reaction with carboxylic acid anhydrides, carboxylic acid chlorides~
sulfonic acid chlorides or chlorophosphates. Examples of these are given in the subsequent production examples.
The hydroxyl compounds used as starting materials are in part obtainable commercially, or can be produced by the methods generally known for the production of 2-(2-hydroxyphenyl)-benzotriazoles.
Novel compounds are for example those compounds of the formula I wherein R3 is a group -(CH2) -CooR9 or -(CH2)n-CON(R O)(R ); and also compounds o the formula II
wherein R is a divalent group of the formula ~(CH2)n~CO~O~(CH2)q~0~CO~~CH2)n~, - (CH2)n-CO-O- (CH2CH20)p-CO- (CH2)n-, (CH ) CO NH R10 NH CO (CH ) - or 2)n CH2 ,CHllcH2-o-(c~2)q-o-cH2-cH-cH2-o-co-(c~I2) _ Examples of individual compounds of the Eormula I are:
2-(2-acetoxy-3-methyl-S-tert-butyl-phenyl)-benzotriazole, 2-[2-acetoxy-3,5-di(tert-butyl)-phenyl]-benzotriazole, 2-~2-propionyloxy-3-isopropyl-5-tert-butyl-phenyl)-benzotriazole, 2-(2-butyroyloxy-3-sec-butyl-5-tert-butyl-phenyl)-benzotriazole, 2-[2~hexanoyloxy-3,5-di(tert-pentyl)-phenyl]-benzotriazole, ~ ,, ~.2~3~55 g
R as a diacyl group-can be for example: oxalyl, succinyl, glutaroyl, adipoyl, 2,2,4-trimethyladipoyl, sebacoyl (octamethylenedicarbonyl), decamethylenedicarbonyl, terephthaloyl or isophthaloyl. R , R3, R , R , R , R
R 3, R 4, R 5 as alkyl can, within the given number of C atoms, be for example: methyl, ethyl, propyl, isopropyl, n butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl or dodecyl.
R and R3 are preferably branched-chain alkyl groups.
R10 and Rll as alkyl interrupted by O or N can be for example: 2-butoxyethyl, 3-methoxypropyl, 3-e~hoxy-propyl, 3-isopropoxypropyl, 3-butylaminopropyl or 3-ethyl-aminopropyl.
. . .
~ ~ ~3 ~5 S
R2, R10 and Rll as alkenyl can be for example: allyl, methallyl or 2-butenyl.
R14 and R15 as alkoxy can be ~or example: methoxy, ethoxy, isopropoxy, butoxy, hexyloxy, octyloxy9 decyloxy or dodecyloxy.
R2 and R3 as halogen can be for example: fluorine, chlorine or bromine.
R , R3, R10 and Rll as cycloalkyl can be for example:
cyclopentyl, cyclohexyl, methylcyclohexyl, cyclooctyl or cyclododecyl.
R2, R3, R10 and Rll as phenylalkyl can be for example:
benzyl, a-methylbenzyl, a-dimethylbenzyl or 2-phenylethyl.
R and R as phenylalkyl are preferably a-dimethylbenzyl.
R~ as alkoxy or alkoxycarbonyl can be for example:
methoxy, ethoxy, isopropoxy, butoxy, hexyloxy, octyloxy, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl or pentyl-oxycarbonyl. Cl-C4-alkoxy or alkoxycarbonyl radicals are preferred.
R7 as alkylene can be for example: methylene, 1,2-ethylene, tri-, tetra-, penta-, hexa-, octa- or deca-methylene.
When R10 and Rll together are alkylene, oxa- or aza-alkylene, they form together with the N atom to which they are bound a heterocyclic ring, for example a pyrrolidine, piperidine, morpholine, piperazine or hexamethylene ring.
R12 can be for example: 1,2-ethylene, tri-, tetra-, penta-, hexa-, octa- or dodecamethylene, 2,4,4-trimethyl-hexamethylene, 3-oxaheptamethylene or 3,6-dioxa-decamethylene.
,:
~L2~3~
Preferred compounds of the formula I are those wherein x = 1, Rl is a group of the formula -Co-R5, -S02-R6 or -P(O) (R 4)(R15), R2 is Cl-C12-alkyl, cyclohexyl or C7-Cg-phenylalkyl, R is Cl-Cl~-alkyl, cyclohexyl, C7 Cg-phenylalkyl or a group -CH2CH2COOR , R is hydrogen, methyl or chlorine, R5 is Cl-cl2~alkYl~ C2-C4-alkenYl' phenyl~
benzyl or naph~hylmethyl, R is methyl, phenyl or C7-C18-alkylphenyl, R9 is Cl-C12-alkyl, and R14 and R15 independently of one another are each Cl-C4-alkoxy, methyl or phenyl. Preferably, R therein is a group -CO-R or -S02-R , R is Cl-C8-alkyl or a-dimethylbenzyl, R is Cl-C8-alkyl, a-dimethylbenzyl or a group -CH2CH2COOR , and R4 is hydrogen or chlorine.
Particularly preerrecl compounds of the ormula I are those wherein x=L, Rl is a group -Co~R5 or -S02-R , R2 is Cl-C8-alkyl or a-dimethylbenzyl, R3 is Cl-C8-alkyl, a-dimethylbenzyl or -CH2CH2COOR , R is hydrogen or chlorine, R is Cl-cl2-alkyL~ C2-C4-alkenyl, phenyl, benzyl or naphthylmethyl, R is methyl, phenyl or C7-C18-alkylphenyl, and R9 is cl-C12-alkyl.
Preferred also are compounds of the formula I wherein x=2, R is a group -Co-R7-Co-, R is Cl-C8-alkyl or a-dimethylbenzyl, R is Cl-C8-alkyl, a-dimethylbenzyl or a group -CH2CH2COOR , R is hydrogen or chlorine, R is C2-C8-alkylene, and R is Cl-C12-alkyl.
: Further preferred compounds are those of the formula II
wherein R is a group -CO-R or -S02-R , R is Cl C8-alkyl : or a-dimethylbenzyl, R is a group of the formula .
CH COO (C~ ) -OCOCH2CH2- o5r -CH2CH2C 2 R is hydrogen or chlorine, R is Cl-C12-alkyl, C2-C~-alkenyl, phenyl, benzyl or naphthylmethyl, R is methyl, phenyl or C7-C18-alkylphenyl~ R12 is C2-C8-alkylene, and q is a number from 2 to 8.
~"
~ 2 ~3~ 5 Some of these compounds are known and some are novel compounds. They can be produced essentially from the corresponding hydroxyl compounds (Rl = H) by esterification of the hydroxyl group, using the customary methods of acylation of phenolic OH groups, for example by reaction with carboxylic acid anhydrides, carboxylic acid chlorides~
sulfonic acid chlorides or chlorophosphates. Examples of these are given in the subsequent production examples.
The hydroxyl compounds used as starting materials are in part obtainable commercially, or can be produced by the methods generally known for the production of 2-(2-hydroxyphenyl)-benzotriazoles.
Novel compounds are for example those compounds of the formula I wherein R3 is a group -(CH2) -CooR9 or -(CH2)n-CON(R O)(R ); and also compounds o the formula II
wherein R is a divalent group of the formula ~(CH2)n~CO~O~(CH2)q~0~CO~~CH2)n~, - (CH2)n-CO-O- (CH2CH20)p-CO- (CH2)n-, (CH ) CO NH R10 NH CO (CH ) - or 2)n CH2 ,CHllcH2-o-(c~2)q-o-cH2-cH-cH2-o-co-(c~I2) _ Examples of individual compounds of the Eormula I are:
2-(2-acetoxy-3-methyl-S-tert-butyl-phenyl)-benzotriazole, 2-[2-acetoxy-3,5-di(tert-butyl)-phenyl]-benzotriazole, 2-~2-propionyloxy-3-isopropyl-5-tert-butyl-phenyl)-benzotriazole, 2-(2-butyroyloxy-3-sec-butyl-5-tert-butyl-phenyl)-benzotriazole, 2-[2~hexanoyloxy-3,5-di(tert-pentyl)-phenyl]-benzotriazole, ~ ,, ~.2~3~55 g
5-chloro~2-[2-octanoyloxy-3,5-di(tert-butyl)-phenyll-benzotriazole, S-methyl-2-(2-benzoyloxy-3,5-dimethyl-phenyl)-benzotriazole, 5-methoxy-2-[2-(4-chlorobenzoyloxy)-3,5-di~tert-butyl)-phenyl]-benzotriazole, 2-[2-p-toluenesulfonyloxy-3~5-di(tert-butyL)-phen benzotriazole, 2-[2-dodecylsulfonyloxy-3,5-di(l,l-dimethylbenzyl)-phenyl]-benzotriazole, 2-[2-(p-dodecyLbenzenesul~onyloxy)-3-sec-butyl-S-tert-butylphenyll-benzotriazole, di-[2-(benzo~riaæol-2-yl)-4,6-di~tert-butyl)-phenyl]-adipate, di-[2-(5-chlorobenzotriazol-2-yl)-4-methgl-6-tert-butyl-phenyl]-isophthalate, ~-~3-(benzotriazol-2-yl)-4-acetoxy-5-tert-butyl-phenyl]-propionic acid methyl ester, ~3-(benzotriazol-2-yl)-4-p-toluenesulfonyloxy-5-tert-butyl-phenyll-acetic acid butyl ester, and ~-[3-(benzotriazol-2-yl)-4-benzoyloxy-5-cyclohexylphenyl]-propionic acid-2-butoxyethyl ester.
Examples of individual compounds of the formula II are:
di-[3-~benzotriazol-2-yl)-4-acetoxy-5-tert-butyl-phenyl-acetic acid ester] of diethylene glycol, di-[~-(3-(benzotriazol-2-yl)-4-p-toluenesulfonyloxy-5-sec-butyl-phenyL)-propionic acid ester] of butanediol-1,4, and M,~'-hexamethylene-bis[~-(3-(benzotriazol-2-yl)-4-butyroyloxy-5-methyl~phenyl)-propionic acid amide~.
~ ~395~i The foLlowing Examples further illustrate the production of compounds such as those listed above.
Production Examples Example A _ Acetylation 100 ml of acetic anhydride are added to l mol of 5-chloro-2-[2-hydroxy-3,5-di(tert-butyl)-phenyl]-benzo-triazole, and the mixture is refluxed (140C). After the addition of o.6 g of dimethylaminopyridine, the mixture is refluxed for a further 7 hours. A specimen shows in the thin-layer chromatogram that no further starting material is present. The excess acetic anhydride is distilled off in vacuo, and the brown residue is d~ssolved in methylene chloride~ The solution is washed with a 5%
Na2C03 solution and with water; it is then dried over Na2S04 and concentrated by evaporation. The crystalline residue is recrystallised from methanol to thus obtain 5-chloro-2-~2-acetoxy-3,5-di(tert-butyL)-phenyll-benzo-triazole in the form of white crystals which melt at 132-134C (compound No. 1).
There are obtained in an analogous manner the following acetoxy compounds of the general formula R4/ ~
. . .
~ ~395~
~ ~ aJ
C E~ ~ ~ E~ ~ ' ~ ~ ~ d o ~ ~ ,~ ~ n ~.~ ,~ ~ ~ . o ,~ D ee~ e e d ~ d d 1~ 1~d d d ~ , oo 'o d o ~ ~ ~ ~ o O 1`
~1 ~ ~ ~ ~ O ~ ~ ~ '~
~ ~ ~ V ~ ~ 0V U CJ ~ ~Q U U U P~ ~, p, e ~ z e e e - -- -m m ~ ' N
ll ~ ~ ,, B ~ ~ , ~ !.~ N ¦
~1 ~ N ~
. ~`J
~;
h ~I h h h u e : -~ rl ~ V
IJ ~ ~ J~l U tn . ~ ~ ~
. __~. _ .
. ~ .
O ~
: ~ S5 ' ' : _ _ :
' .
.,~.
~ ~c;3 ~3 Example_B - Tosylation C.l mol of 2-(2-hydroxy-3-sec-butyl-5--tert-butyl-phenyl)-benzotriazole is dissolved in 200 ml of toluene. There is then added, with stirring, a solution of 20 g of NaOH in 20 g of water and 0.01 mol of tetrabutylammonium hydrogen sulfate (as phase-transfer catalyst), in the course of which the organic phase assumes an intense yellowish-orange colour. A solution of 0.11 mol of p-toluenesulfonyl chloride in 50 ml of toluene is then slowly added dropwise at room temperature. The exothermic reaction is compensated for by cooling with ice-water. The mixture is subsequently stirred for 3 hours at room temperature, during which time the colour of the toluene solution gradually disappears. A
specimen indicates .in the thin-layer chromatogram that no further starting material is present. The reaction mixture is poured into 1 litre of ice-water; the organic phase is separated, washed twice with 300 ml of water each time and dried over Na2S04. The solution is concentrated in vacuo, and the residue is crystallised from ethanol to thus obtain 2-(2-toluenesulfonyloxy-3-sec-butyl-5-tert-butyL-phenyl)-benzotriazole in the form of white crystals which melt at 139-141C ~compound No. 11).
There are obtained in an analogous manner the following sulfonates of the general formula . .
N
R4 ~- ~11/ \R3 :;
.
..
39rl5 ~ 13 --... , ~ ~ ' .,.
,1 ~ o h ~d ~e ~ 6`e B`e ~ ~ ~;~
'~ ~ ~ O U~ CO
O O o o ~ ra ~: ~ h h ~ ,C ~:: C~ d ~
`~ '`'OOOOOOOOOoo tJ ,~ o I~
I I ~ Oco ~ ~ O `;t ~--.~ ~ o ~ o ~
~: ~1 ~ ~ ~1 ~1 ~ ~ ~ ~ ~ ~ ~ ~ .-1~1 P~ p~ d o Ei ,~ ~3 E C~ Z ~ ~ Z c~ ~ Z E3 . ._ _ -:~ ~
,~ U
,~ ~ ,~ ~ ~ :~ ~ ~ P~ ~ ~ ~ ~
o o o o ~ ~ ~ o . ~ ~ ~ ~
.,, o '~
u d a~ ~ d ~ ~ ~ a ~ ._ . ~ .
~ ~ ~ a ~ , 3 a a~
. v ,13 ~ ~, h v v ~ ~ o -- .
, ~
~ ~ ~ 1~ 0~
O ~ . -- - - _.
., ,~
, ....
~X~3~S~i The bis-tosylate of the following formula is produced in an analogous manner:
O SO ~ CH CH3-~ S2-"~ CH2CH2CONH-(CH2)6-NHCOCH2CH2 (compound No. 24~ m.p.: 215-217C.
Example C - Esterification with acid chloride 0.12 mol of triethylamine is added to a solution of 0.08 mol of 2-[2-hydroxy-3,5-di(tert-butyl)-phenylJ-benzotriaæole in lS0 ml of methylene chloride. To this solution is slowly added clropwise at L0-15C, w:lth stirring, a solution of 0.08 mol of 2-naphthylacetyl chloride in 50 ml of methylene chloride. The temperature is then allowed to rise to 20-25C, and the mixture is stirred for 6 hours at this temperature. The triethylammonium chloride which has precipitated is filtered off, and the filtrate is washed with water, dried over Na2S04 and concentrated by evapor-ation. The crystalline, reddish-coloured residue is recrystallised from hexane to thus obtain 2-~2~ naphthyl-acetoxy)-3,5-di~tert-butyl~-phenyl]-benzotriazole in the form of white crystals which melt at 150-151C
(compound No. 25).
There are obtained in an analogous manner the following phenol esters of the general formula N>I\R3 ~: ~
`, :
. , ~39~
~. ~ o ~ ~ ~o ~o o r~ I I ~ I 0!~ 1 1 1 1 0 ~ ~ I~ ~ ~ ~ I ~ I~D.J ~0~ 1 r~ C~J r~ ~r ~ o ~ ~ ~ O O O
u~ ~ ,~r~ ,1 ~ o~ ,~co ~ ~,~ ~ ~
P~
N N
v d ~ ~ g ~J ~ ~ ~ d :- g ~ r~ I rp v~J.J
h V ~ I
~ C ~ ~ C
.~ e ~
~ V V ~ rl N J~ rl N ~1 t`l O ~
~ v~ ~ v ~ D ~ ~ ~:3 D J
_ _ r _ I
O ~;\0 3/~ o// \-0 ~ ~, \
:: ~ l gl c~ lv o ~ ~ q :c o o o oo o o o o o o o ~p~ c~ y ~ l l y l ~ l --- ~ --~ ~D 1` CO ~ O ~I N ~ ~ ~ ~ . CO
O t`l ~1 J N ~ r~ r~ ') ~) ~ ~ ~ ~
.
`
,....
3~5 Exam~le D - Esterification with acid chlorides by phase-transfer catal sis Y
0.1 mol of 2-[2-hydroxy-3,5-di(tert-butyl)-phenyl]-benzotriazole is dissolved in 150-200 ml of toluene. To the solution are added 20 g of NaOH dissolved in 20 ml of water (50% NaOH solution) and 0.01 mol of tetrabu~ylammonium hydrogen sulfate (PTC). There is immediately formed an orange-coloured emulsion, and this is heated to ~0C. At this temperature is slowly added dropwise a solution of 0.11 mol of chloroformic acid butyl ester in about 30 ml of toluene. The reaction proceeds exothermically, and from 45-50C it is cooled with ice-water. At the end o~ the dropwise addition, the reactlon solution has become ligh~-yellow. Stirring is maintalned for a urther 2 ho~lrs, after which time no further starting product can be identified in the thin-layer chromatogram. The reaction solution is cooled to room temperature, and about 200 ml of water are added. The organic phase is then separated and is washed twice with 100 ml of water each time. The toluene solution is dried with sodium sulfate and is afterwards concentrated in a rotary evaporator. The light-yellow residue is recrystallised from ethanol to thus obtain 2-l2-(butoxy-carbonyloxy)-3,5-di~tert-butyl)-phenyl]-benzotriazole (compound No. 39) in the form of white crystals which melt at 116-118C.
By variation of the acid chloride, there are obtained in an analogous manner the following phenolic esters:
R O~ ,,R
\ /
,, .
9~5 .
~e ~ ~ ~ ~ ~ ~ ~ ~ ~ E~ ~ ~ b~ ~ ~ ~ 6`~
a~ ~ ~ O
o oo a~ D `D ~ O 0~~ ~ CO O~
r_ I~ ~ o;~ ~ r~
! ~ o o o o o o o o o ~ o o o o o ~ o o J ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~o ~ ~ ~ E~
O ~~ I~ ~ ~D ~ O u~ O ~ ~ ~ ~ O ~
o ~ Oo~ ~ ~ r~ ~ ~ ô oo ,~" t~ ) u o ~ V ~
~: z ~ z c~ p: z c~ ~ z - -~
N N
~ V ~ V ' V
0 ~
~ rl N J'~ ~l N ~ ~
~1~ h ~ h _ - ... . ~
, . I
:: : ~ ~0~0 ~ ' ~ .~ 0~r ~r o o 0 1 , ~ .1.
O o ,( ~ ~ ~ U~ ~D
o O _ . _ _ _ _ _ 1~ ~3~
. . _ r~ I~ o r~ ) d R ~ ~ ~ a a O ~~ ~ ~ ~ ~ o o ~c~ ~1~ o u~ ~ ,1 . , .... C~ U~ C~l I~ ~ ~ ~I I I I I I I
O o~ ~ ~ ;r o~
æ c~ z _ 11 d ~ d d ~7 c~
o ~ d ~ ~ d ~ O
~ V ,E~ ~ P
~ 'C) ~ ~ ~ ~ ~ h ~ c ~ Q\
_ ~ _ V ~ ~ , ~ ~ N ~J ~
~ ~ d ~ ~~ d ~ h _ ~ D V V JJ ~ IJ U ,~ ~ IJ
f,l . ~., : ~
N N N N N ~
0 ~
~: y y 0~ ~ 0~ CO~ y y y y ' ~
; ~a :
O r-- o~ cn O ~I N ~
n _ _ _ _ _ _ _ _ , . ~
~3~:3SS
..~
E~ ~ ~
~: o o o lJ B~
~ o r~
o U~ , . . . , .,, ' ~ . ,, u~ ,, , c~ c~ o ! ~
C`l 1~ ~
_ ~/;\../;\~o//\. , I 11 t ~1 1 11 \\o/~ ;\o/~
o ~ I~/;\o : ~ // \. .// \0 .// \. , !: : ~ 1l !
/~O~o/
u~
:
..
,. . .
3~3r~
Y
O - - o o ~d co O O C~l O = ~ ~ P~
~ \\o~ ~ ~ ~
~ ~1 ¦ , 3 ~ .
V
r O
~, Z
_ ,.
1 2 ~3~3~5 The coating materials according to the invention can be pigmented or unpigmented. They contain as the main component a binder which is initially a soluble resin and which7 after application, is converted into an insoluble state. Curing can be effected either by heating or by a chemical reaction. Examples o~ such binders are: alkyl resins, acrylic resins, epoxide resins, melamine resins, urea resins, polyurethanes, polyesters or phenolic resins, and mixtures thereof with one another.
The coating material is usually applied as a solut-ion.
Coating materials with a small amount of solvent (high sclids) or without solvent (with the addition of reactive diluents) have recently become of increasing importance in coating practice. In all cases, the addition oE a light stabiliser can be of interest. Examp:Les in this respect are surface lacquers Eor multilayer coatings, which lacquers are intended to protect the pigmented lower layer against damage by light. Surface coatings of this type are used in particular in vehicle construction.
~urther examples are UV protective lacquers for furniture or for plastic films or sheets. The present invention is of special importance with regard to coating materials which on application come into contact with copper or with copper alloys.
Depending on the purpose of their application, the coating materials can contain, besides pigments and solvents, other additives, for example flow-control agents, thixotropic agents, wetting agents, metal deactivators or antioxidants. They can aLso contain, in addition to the crypto light stabiliser according to the invention, a further light stabiliser from the class of stericallg hindered amines, since these likewise do not absorb in the ~UV range of 330 - 400 nm.
..:
~ ~39SS
The coating materials according to the invention can be applied to any desired substrates, for example to metal, glass, ceramic, wood, paper or plastic surfaces.
The application is effected by the customary methods for coating materials, for example by brushing, immer~ion or spraying, or by electrostatic processes. The degree of activation of the light stabiliser is governed by the extent to which short-wave light acts on the coating.
With a low level of irradiation, there will therefore occur a slow activation, whereas intensive irradiation wi].l result in a rapid activation. The light stabiliser can also be artificially activated by exposing the coating before its applicatlon to UV light. This can be carried out beore or a~ter the curing of the coating. The manner in which curing is efected will depend on the nature of the employed binder, for example by heating or by oxidative curing.
The following Examples illustrate the application according to the invention of crypto light stabilisers.
Except where otherwise stated, the symbol % denotes per cent by weight.
Example 1: Stabilisation of a two-layer metallic-effect lacquer Aluminium sheets 0.5 mm in thickness are coate~ with an aluminium-pigmented base lacquer based on polyester/
cellulose acetobutyrate/melamine resin. There is then sprayed onto the wet base lacquer a clear lacquer of the following composition:
58.3 parts of Viacryl ~ VC 373 (acrylic resin, Vianova, Vienna), 27.3 parts of Maprenal ~ MF 590 (melamine resin, Hochst A&~ Frankfurt), ~X~;3 3 1.0 part of a 1% solution of a silicone oil in xylene, 4.0 part of Solvesso ~ 150 (aromatic solvent mixture), 5.4 parts of xylene, and 4.0 parts of ethyl glycol acetate.
Also added is 0.9 part of the crypto light stabiliser given in Table 1, corresponding to 2% relative to the binder. The viscosity of this clear lacquer is adjusted to 21 sec/DIN cup 4. It is applied in a dry~layer thickness of 40 ~m, and is stoved at 130C for 30 minutes.
The specimens are in the one case weathered in a QUV rapid weatherometer (Fa. Q-Panel) and in the other case in a Xenotes~ ~ 1200 (Fa. Heraeus) up to 5200 hours.
After 800 hours ln each case, the 20 gLoss according to DIN 67530 is measured, and the surface of the specimens is examined for cracking under the stereomicroscope.
As a basis of comparison, there is used a) an unstabilised specirnen, and b) a non-blocked W absorber of the formula ~ f 4 9 comparison A
CH2cH2co(ocH2cH2)moH
(m~ 7 ) The results are surnrnarised in Tables 1 and 2.
Tab e 1 - Q~V - 2 - Weathering I
Light ~ 20 gloss after Cracking ¦ stabiliser o 1600 3200 4800 h ` after l _ _ , none 91 42 _ _ 2800 h compound No~2 91 79 76: 26 5200 h comparison A go 81 69 29 5200 h I _ i3~3~55 - 2~ -Table 2 Xenotest ~ 1200 - Weatherin~
_ Light 20 gloss after Cracking stabiliser noticeable o 1600 32004800 h after _ . _ without 91 38 31 _ 3600 h compoundNo.2 91 ~8 54 31 5200 h comparison A go 61 44 28 5200 h As can be seen from the Tables~ the protective action of ~he crypto light stabiliser is approximately equal to that of the non-blocked light stabil:iser.
Example 2: Discoloration_as a resuLt of contact with copper.
The clear lacquer described in Example 1 is brought into contact, before its application, for 48 hours with a copper sheet. The lacquer is then applied in a layer thickness of 40 ~m to sheets which have been primed with a TiO2-pigmented white lacquer based on polyester resin.
The specimens are subsequently stoved for 30 minutes at 130C.
The discoloration of the specimens is measured in the one case according to the Yellowness Index (YI) and in the other case according to DIN 6174 (as ~ E).
There is used as a comparison the commercial W absorber 2-[2-hydroxy-3,5-di-(1,1-dimethylbenzyl)-phenyll-benzo--triazole = comparison B.
The results are summarised in Table 3.
~ ~395~j Table 3 Light stabiliser _ _ none 3.4 2.1 1% of compound No. 2 3.1 2.0 1% of comparison B 5.8 3.2 It is seen from the TabLe that the free hydroxyphenyl-benzotriazole causes a yellowing, whereas the crypto light stabiliser does not.
Example 3: Stora~e stability o~ the crypto ~i&~
stabilisers Methanol soLutions 5.10 5 mol/l o~ a benzotriazole derivatlve are stored for 14 days in darkness. The UV spectrum of the solutions is measured before and after storage. The solutions of the compounds Nos. 2, 5, 6, 7, 8, 11, 12, 13, 14, 15, 17 and 18 exhibit no alteration of the spectrum.
Similar blocked benzotriazole derivatives, which are unsubstituted in the ortho-position with respect to the blocked OH group, exhibit after storage an alteration of the spectrum, which indicates that a partial unblocking has occurred during storage in darkness.
Example 4: A two-component stoving lacquer based on acrylic resin is prepared from the following components:
Portion A:
72.8 g of an amine-functional acrylic resin (Setalux ~ 83-03 BX 55, Fa. Synthese, Netherlands), 0.9 g of a flow-control agent based on silicone oil ;~ (Baysilon ~ oil, Fa. Bayer AG), and 9.0 ~ of xylene 82.7 g , :
63~35 Portion B-17.3 g of an epoxy-functional acrylic resin (Setalux ~ 83-04 55 70, Fa. Synthese, NL).
The portions A and B are combined, and a solution of the light stabiliser given in Table 4 in xylene is added.
This lacquer ls sprayed onto a metal sheet which is primed with a silver-metallic stoving lacquer based on polyester/
cellulose acetobutyrate/melamine resin. After exposure to the air at room temperature for one hour, the specimens are stoved for 30 minutes at 135C. The Layer thickness of the surface lacquer is about 40 /um.
The discoloration occurring on stovlng is me~sured according to DIN 6174 as shade clifference ~ E.
There are compared in each case the free hydroxy-benzotriazoles and the 0-acyl compounds thereof.
Table 4 Li~ht stabiliser E
none 0 7 _ 2% of compound No. 8 1.0 2% of comparison B 12.8 2% of compound No. 6 0.7 2% of comparison C 4.4 comparison B = 2-[2-hydroxy-3,5-di(l~l-dimethylbenzyl)-phenyl]-benzotriazole comparison,C = 2 ~2-hydroxy-3,5-di(tert-pentyl) phenyl]-~ ~ benzotriazoLe.
: :
' , ,.
, .
~ ~j3 ~5 Example 5 - Discoloration on weatherin~
The clear lacquer described in Example 1 is applied in a dry-film thickness of 40,um to metal sheet primed white. The specimens are stoved at 130C for 30 minutes and then weathered in a Florida apparatus for 3 months.
The degree of whiteness according to DIN 6174 is measured before and after weathering, and from the result is determined in each case the shade difference ~\E. The results are summarised in Table 5.
Table 5 Light stabiliser ~ E
none 3.2 2% of compound No. 6 1.0 2% of compound No. 13 0.8 2% of compound No. 20 o.6 2% of compound No. 46 1.0 2% of compound No. 52 1.2 xample 6 - Combination with a catalyst which can be cleaved_~y W
A acid-curable acrylic resin/melamine resin clear lacquer is prepared from:
57.3 parts o Acryloid ~ AT 410 (acrylic resin, Rohm and Haas Corp., USA) (75% solids content), 18.0 parts of Cymel ~ 301 (melamine resin, Amer. Cyanamid), 10.0 parts of butylacetate, 1.8 parts of cellulose acetobutyrate CAB 551 (Eastman Chem. Corp.), 2.6 parts of a flow-control agent (Modaflow ~ , Monsanto Corp.) and 10.5 parts of butanol.
The solids content of the lacquer is 653/3. The lacquer 35.
is knife-coated in a dry-film thickness of 40 ~m onto glass plates. The specimens are irradiated for 10 seconds with a 160 W W -lamp, and then stoved at 120C for 30 minutes.
There is used as a curing catalyst tha~ can be activated by W light 1% of benzoin-p-toluenesulfonate, which cleaves off p-toluenesulfonic acid on exposure to UV light. A blocked acid catalyst of this type has the advantage that it eEfects no curing in darkness. It has the disadvantage that in the presence of W-absorber light stabilisers the curing of the lacquer is incomplete. When however there is used as light stabilisers the 0-acylated benzotriazoles according to the invention, the activity of the curing catalyst is not hindered, as is shown by the ~ollowing Table 6. The curing o~ the lacquer is assessed in these tests by measurement of the pendulum hardness according to DIN 53157. The specimens are subsequently weathered in the Xenon Weatherometer, and the percentage gloss retention is thus determined.
Table 6 Light stabiliserGloss retention in % Pendulum after weathering of hardness 1000 h 2000 h 3000 h (sec) ~ . ~
none 83 S - 204 *
1% of comparison C 91 82 4 78 1% of compound No. 2 70 56 2 154 lZ of compound No. 5 75 77 6 lSS
1% of compound No. S
+ 1% of HALS*'~ 102 63 23 122 1% of compound No. 6 98 78 S 158 , ...
1~3'3'jS
) comparison C = 2-~-hydroxy-3,5-di-tert-pentyl-pheny~-benzotriazole (Tinuvin 328) **) HALS = 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4,5]decanedione-2,4 (Tinuvin ~ 440) : It is seen from the above that the free benzotriazole (comparison C) does provide good protection against light but greatly reduces the curing of the lacquer. With the light stabilisers according to the invention there is however obtained both a good protection against light ~ :and satisfactory curing. The level of protection against : : : light can be increased by the addition o a light stab:iliser : ~ of the sterically hindered amine type (HALS)~
,~:~: : :
' ~ :
., :
.
Examples of individual compounds of the formula II are:
di-[3-~benzotriazol-2-yl)-4-acetoxy-5-tert-butyl-phenyl-acetic acid ester] of diethylene glycol, di-[~-(3-(benzotriazol-2-yl)-4-p-toluenesulfonyloxy-5-sec-butyl-phenyL)-propionic acid ester] of butanediol-1,4, and M,~'-hexamethylene-bis[~-(3-(benzotriazol-2-yl)-4-butyroyloxy-5-methyl~phenyl)-propionic acid amide~.
~ ~395~i The foLlowing Examples further illustrate the production of compounds such as those listed above.
Production Examples Example A _ Acetylation 100 ml of acetic anhydride are added to l mol of 5-chloro-2-[2-hydroxy-3,5-di(tert-butyl)-phenyl]-benzo-triazole, and the mixture is refluxed (140C). After the addition of o.6 g of dimethylaminopyridine, the mixture is refluxed for a further 7 hours. A specimen shows in the thin-layer chromatogram that no further starting material is present. The excess acetic anhydride is distilled off in vacuo, and the brown residue is d~ssolved in methylene chloride~ The solution is washed with a 5%
Na2C03 solution and with water; it is then dried over Na2S04 and concentrated by evaporation. The crystalline residue is recrystallised from methanol to thus obtain 5-chloro-2-~2-acetoxy-3,5-di(tert-butyL)-phenyll-benzo-triazole in the form of white crystals which melt at 132-134C (compound No. 1).
There are obtained in an analogous manner the following acetoxy compounds of the general formula R4/ ~
. . .
~ ~395~
~ ~ aJ
C E~ ~ ~ E~ ~ ' ~ ~ ~ d o ~ ~ ,~ ~ n ~.~ ,~ ~ ~ . o ,~ D ee~ e e d ~ d d 1~ 1~d d d ~ , oo 'o d o ~ ~ ~ ~ o O 1`
~1 ~ ~ ~ ~ O ~ ~ ~ '~
~ ~ ~ V ~ ~ 0V U CJ ~ ~Q U U U P~ ~, p, e ~ z e e e - -- -m m ~ ' N
ll ~ ~ ,, B ~ ~ , ~ !.~ N ¦
~1 ~ N ~
. ~`J
~;
h ~I h h h u e : -~ rl ~ V
IJ ~ ~ J~l U tn . ~ ~ ~
. __~. _ .
. ~ .
O ~
: ~ S5 ' ' : _ _ :
' .
.,~.
~ ~c;3 ~3 Example_B - Tosylation C.l mol of 2-(2-hydroxy-3-sec-butyl-5--tert-butyl-phenyl)-benzotriazole is dissolved in 200 ml of toluene. There is then added, with stirring, a solution of 20 g of NaOH in 20 g of water and 0.01 mol of tetrabutylammonium hydrogen sulfate (as phase-transfer catalyst), in the course of which the organic phase assumes an intense yellowish-orange colour. A solution of 0.11 mol of p-toluenesulfonyl chloride in 50 ml of toluene is then slowly added dropwise at room temperature. The exothermic reaction is compensated for by cooling with ice-water. The mixture is subsequently stirred for 3 hours at room temperature, during which time the colour of the toluene solution gradually disappears. A
specimen indicates .in the thin-layer chromatogram that no further starting material is present. The reaction mixture is poured into 1 litre of ice-water; the organic phase is separated, washed twice with 300 ml of water each time and dried over Na2S04. The solution is concentrated in vacuo, and the residue is crystallised from ethanol to thus obtain 2-(2-toluenesulfonyloxy-3-sec-butyl-5-tert-butyL-phenyl)-benzotriazole in the form of white crystals which melt at 139-141C ~compound No. 11).
There are obtained in an analogous manner the following sulfonates of the general formula . .
N
R4 ~- ~11/ \R3 :;
.
..
39rl5 ~ 13 --... , ~ ~ ' .,.
,1 ~ o h ~d ~e ~ 6`e B`e ~ ~ ~;~
'~ ~ ~ O U~ CO
O O o o ~ ra ~: ~ h h ~ ,C ~:: C~ d ~
`~ '`'OOOOOOOOOoo tJ ,~ o I~
I I ~ Oco ~ ~ O `;t ~--.~ ~ o ~ o ~
~: ~1 ~ ~ ~1 ~1 ~ ~ ~ ~ ~ ~ ~ ~ .-1~1 P~ p~ d o Ei ,~ ~3 E C~ Z ~ ~ Z c~ ~ Z E3 . ._ _ -:~ ~
,~ U
,~ ~ ,~ ~ ~ :~ ~ ~ P~ ~ ~ ~ ~
o o o o ~ ~ ~ o . ~ ~ ~ ~
.,, o '~
u d a~ ~ d ~ ~ ~ a ~ ._ . ~ .
~ ~ ~ a ~ , 3 a a~
. v ,13 ~ ~, h v v ~ ~ o -- .
, ~
~ ~ ~ 1~ 0~
O ~ . -- - - _.
., ,~
, ....
~X~3~S~i The bis-tosylate of the following formula is produced in an analogous manner:
O SO ~ CH CH3-~ S2-"~ CH2CH2CONH-(CH2)6-NHCOCH2CH2 (compound No. 24~ m.p.: 215-217C.
Example C - Esterification with acid chloride 0.12 mol of triethylamine is added to a solution of 0.08 mol of 2-[2-hydroxy-3,5-di(tert-butyl)-phenylJ-benzotriaæole in lS0 ml of methylene chloride. To this solution is slowly added clropwise at L0-15C, w:lth stirring, a solution of 0.08 mol of 2-naphthylacetyl chloride in 50 ml of methylene chloride. The temperature is then allowed to rise to 20-25C, and the mixture is stirred for 6 hours at this temperature. The triethylammonium chloride which has precipitated is filtered off, and the filtrate is washed with water, dried over Na2S04 and concentrated by evapor-ation. The crystalline, reddish-coloured residue is recrystallised from hexane to thus obtain 2-~2~ naphthyl-acetoxy)-3,5-di~tert-butyl~-phenyl]-benzotriazole in the form of white crystals which melt at 150-151C
(compound No. 25).
There are obtained in an analogous manner the following phenol esters of the general formula N>I\R3 ~: ~
`, :
. , ~39~
~. ~ o ~ ~ ~o ~o o r~ I I ~ I 0!~ 1 1 1 1 0 ~ ~ I~ ~ ~ ~ I ~ I~D.J ~0~ 1 r~ C~J r~ ~r ~ o ~ ~ ~ O O O
u~ ~ ,~r~ ,1 ~ o~ ,~co ~ ~,~ ~ ~
P~
N N
v d ~ ~ g ~J ~ ~ ~ d :- g ~ r~ I rp v~J.J
h V ~ I
~ C ~ ~ C
.~ e ~
~ V V ~ rl N J~ rl N ~1 t`l O ~
~ v~ ~ v ~ D ~ ~ ~:3 D J
_ _ r _ I
O ~;\0 3/~ o// \-0 ~ ~, \
:: ~ l gl c~ lv o ~ ~ q :c o o o oo o o o o o o o ~p~ c~ y ~ l l y l ~ l --- ~ --~ ~D 1` CO ~ O ~I N ~ ~ ~ ~ . CO
O t`l ~1 J N ~ r~ r~ ') ~) ~ ~ ~ ~
.
`
,....
3~5 Exam~le D - Esterification with acid chlorides by phase-transfer catal sis Y
0.1 mol of 2-[2-hydroxy-3,5-di(tert-butyl)-phenyl]-benzotriazole is dissolved in 150-200 ml of toluene. To the solution are added 20 g of NaOH dissolved in 20 ml of water (50% NaOH solution) and 0.01 mol of tetrabu~ylammonium hydrogen sulfate (PTC). There is immediately formed an orange-coloured emulsion, and this is heated to ~0C. At this temperature is slowly added dropwise a solution of 0.11 mol of chloroformic acid butyl ester in about 30 ml of toluene. The reaction proceeds exothermically, and from 45-50C it is cooled with ice-water. At the end o~ the dropwise addition, the reactlon solution has become ligh~-yellow. Stirring is maintalned for a urther 2 ho~lrs, after which time no further starting product can be identified in the thin-layer chromatogram. The reaction solution is cooled to room temperature, and about 200 ml of water are added. The organic phase is then separated and is washed twice with 100 ml of water each time. The toluene solution is dried with sodium sulfate and is afterwards concentrated in a rotary evaporator. The light-yellow residue is recrystallised from ethanol to thus obtain 2-l2-(butoxy-carbonyloxy)-3,5-di~tert-butyl)-phenyl]-benzotriazole (compound No. 39) in the form of white crystals which melt at 116-118C.
By variation of the acid chloride, there are obtained in an analogous manner the following phenolic esters:
R O~ ,,R
\ /
,, .
9~5 .
~e ~ ~ ~ ~ ~ ~ ~ ~ ~ E~ ~ ~ b~ ~ ~ ~ 6`~
a~ ~ ~ O
o oo a~ D `D ~ O 0~~ ~ CO O~
r_ I~ ~ o;~ ~ r~
! ~ o o o o o o o o o ~ o o o o o ~ o o J ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~o ~ ~ ~ E~
O ~~ I~ ~ ~D ~ O u~ O ~ ~ ~ ~ O ~
o ~ Oo~ ~ ~ r~ ~ ~ ô oo ,~" t~ ) u o ~ V ~
~: z ~ z c~ p: z c~ ~ z - -~
N N
~ V ~ V ' V
0 ~
~ rl N J'~ ~l N ~ ~
~1~ h ~ h _ - ... . ~
, . I
:: : ~ ~0~0 ~ ' ~ .~ 0~r ~r o o 0 1 , ~ .1.
O o ,( ~ ~ ~ U~ ~D
o O _ . _ _ _ _ _ 1~ ~3~
. . _ r~ I~ o r~ ) d R ~ ~ ~ a a O ~~ ~ ~ ~ ~ o o ~c~ ~1~ o u~ ~ ,1 . , .... C~ U~ C~l I~ ~ ~ ~I I I I I I I
O o~ ~ ~ ;r o~
æ c~ z _ 11 d ~ d d ~7 c~
o ~ d ~ ~ d ~ O
~ V ,E~ ~ P
~ 'C) ~ ~ ~ ~ ~ h ~ c ~ Q\
_ ~ _ V ~ ~ , ~ ~ N ~J ~
~ ~ d ~ ~~ d ~ h _ ~ D V V JJ ~ IJ U ,~ ~ IJ
f,l . ~., : ~
N N N N N ~
0 ~
~: y y 0~ ~ 0~ CO~ y y y y ' ~
; ~a :
O r-- o~ cn O ~I N ~
n _ _ _ _ _ _ _ _ , . ~
~3~:3SS
..~
E~ ~ ~
~: o o o lJ B~
~ o r~
o U~ , . . . , .,, ' ~ . ,, u~ ,, , c~ c~ o ! ~
C`l 1~ ~
_ ~/;\../;\~o//\. , I 11 t ~1 1 11 \\o/~ ;\o/~
o ~ I~/;\o : ~ // \. .// \0 .// \. , !: : ~ 1l !
/~O~o/
u~
:
..
,. . .
3~3r~
Y
O - - o o ~d co O O C~l O = ~ ~ P~
~ \\o~ ~ ~ ~
~ ~1 ¦ , 3 ~ .
V
r O
~, Z
_ ,.
1 2 ~3~3~5 The coating materials according to the invention can be pigmented or unpigmented. They contain as the main component a binder which is initially a soluble resin and which7 after application, is converted into an insoluble state. Curing can be effected either by heating or by a chemical reaction. Examples o~ such binders are: alkyl resins, acrylic resins, epoxide resins, melamine resins, urea resins, polyurethanes, polyesters or phenolic resins, and mixtures thereof with one another.
The coating material is usually applied as a solut-ion.
Coating materials with a small amount of solvent (high sclids) or without solvent (with the addition of reactive diluents) have recently become of increasing importance in coating practice. In all cases, the addition oE a light stabiliser can be of interest. Examp:Les in this respect are surface lacquers Eor multilayer coatings, which lacquers are intended to protect the pigmented lower layer against damage by light. Surface coatings of this type are used in particular in vehicle construction.
~urther examples are UV protective lacquers for furniture or for plastic films or sheets. The present invention is of special importance with regard to coating materials which on application come into contact with copper or with copper alloys.
Depending on the purpose of their application, the coating materials can contain, besides pigments and solvents, other additives, for example flow-control agents, thixotropic agents, wetting agents, metal deactivators or antioxidants. They can aLso contain, in addition to the crypto light stabiliser according to the invention, a further light stabiliser from the class of stericallg hindered amines, since these likewise do not absorb in the ~UV range of 330 - 400 nm.
..:
~ ~39SS
The coating materials according to the invention can be applied to any desired substrates, for example to metal, glass, ceramic, wood, paper or plastic surfaces.
The application is effected by the customary methods for coating materials, for example by brushing, immer~ion or spraying, or by electrostatic processes. The degree of activation of the light stabiliser is governed by the extent to which short-wave light acts on the coating.
With a low level of irradiation, there will therefore occur a slow activation, whereas intensive irradiation wi].l result in a rapid activation. The light stabiliser can also be artificially activated by exposing the coating before its applicatlon to UV light. This can be carried out beore or a~ter the curing of the coating. The manner in which curing is efected will depend on the nature of the employed binder, for example by heating or by oxidative curing.
The following Examples illustrate the application according to the invention of crypto light stabilisers.
Except where otherwise stated, the symbol % denotes per cent by weight.
Example 1: Stabilisation of a two-layer metallic-effect lacquer Aluminium sheets 0.5 mm in thickness are coate~ with an aluminium-pigmented base lacquer based on polyester/
cellulose acetobutyrate/melamine resin. There is then sprayed onto the wet base lacquer a clear lacquer of the following composition:
58.3 parts of Viacryl ~ VC 373 (acrylic resin, Vianova, Vienna), 27.3 parts of Maprenal ~ MF 590 (melamine resin, Hochst A&~ Frankfurt), ~X~;3 3 1.0 part of a 1% solution of a silicone oil in xylene, 4.0 part of Solvesso ~ 150 (aromatic solvent mixture), 5.4 parts of xylene, and 4.0 parts of ethyl glycol acetate.
Also added is 0.9 part of the crypto light stabiliser given in Table 1, corresponding to 2% relative to the binder. The viscosity of this clear lacquer is adjusted to 21 sec/DIN cup 4. It is applied in a dry~layer thickness of 40 ~m, and is stoved at 130C for 30 minutes.
The specimens are in the one case weathered in a QUV rapid weatherometer (Fa. Q-Panel) and in the other case in a Xenotes~ ~ 1200 (Fa. Heraeus) up to 5200 hours.
After 800 hours ln each case, the 20 gLoss according to DIN 67530 is measured, and the surface of the specimens is examined for cracking under the stereomicroscope.
As a basis of comparison, there is used a) an unstabilised specirnen, and b) a non-blocked W absorber of the formula ~ f 4 9 comparison A
CH2cH2co(ocH2cH2)moH
(m~ 7 ) The results are surnrnarised in Tables 1 and 2.
Tab e 1 - Q~V - 2 - Weathering I
Light ~ 20 gloss after Cracking ¦ stabiliser o 1600 3200 4800 h ` after l _ _ , none 91 42 _ _ 2800 h compound No~2 91 79 76: 26 5200 h comparison A go 81 69 29 5200 h I _ i3~3~55 - 2~ -Table 2 Xenotest ~ 1200 - Weatherin~
_ Light 20 gloss after Cracking stabiliser noticeable o 1600 32004800 h after _ . _ without 91 38 31 _ 3600 h compoundNo.2 91 ~8 54 31 5200 h comparison A go 61 44 28 5200 h As can be seen from the Tables~ the protective action of ~he crypto light stabiliser is approximately equal to that of the non-blocked light stabil:iser.
Example 2: Discoloration_as a resuLt of contact with copper.
The clear lacquer described in Example 1 is brought into contact, before its application, for 48 hours with a copper sheet. The lacquer is then applied in a layer thickness of 40 ~m to sheets which have been primed with a TiO2-pigmented white lacquer based on polyester resin.
The specimens are subsequently stoved for 30 minutes at 130C.
The discoloration of the specimens is measured in the one case according to the Yellowness Index (YI) and in the other case according to DIN 6174 (as ~ E).
There is used as a comparison the commercial W absorber 2-[2-hydroxy-3,5-di-(1,1-dimethylbenzyl)-phenyll-benzo--triazole = comparison B.
The results are summarised in Table 3.
~ ~395~j Table 3 Light stabiliser _ _ none 3.4 2.1 1% of compound No. 2 3.1 2.0 1% of comparison B 5.8 3.2 It is seen from the TabLe that the free hydroxyphenyl-benzotriazole causes a yellowing, whereas the crypto light stabiliser does not.
Example 3: Stora~e stability o~ the crypto ~i&~
stabilisers Methanol soLutions 5.10 5 mol/l o~ a benzotriazole derivatlve are stored for 14 days in darkness. The UV spectrum of the solutions is measured before and after storage. The solutions of the compounds Nos. 2, 5, 6, 7, 8, 11, 12, 13, 14, 15, 17 and 18 exhibit no alteration of the spectrum.
Similar blocked benzotriazole derivatives, which are unsubstituted in the ortho-position with respect to the blocked OH group, exhibit after storage an alteration of the spectrum, which indicates that a partial unblocking has occurred during storage in darkness.
Example 4: A two-component stoving lacquer based on acrylic resin is prepared from the following components:
Portion A:
72.8 g of an amine-functional acrylic resin (Setalux ~ 83-03 BX 55, Fa. Synthese, Netherlands), 0.9 g of a flow-control agent based on silicone oil ;~ (Baysilon ~ oil, Fa. Bayer AG), and 9.0 ~ of xylene 82.7 g , :
63~35 Portion B-17.3 g of an epoxy-functional acrylic resin (Setalux ~ 83-04 55 70, Fa. Synthese, NL).
The portions A and B are combined, and a solution of the light stabiliser given in Table 4 in xylene is added.
This lacquer ls sprayed onto a metal sheet which is primed with a silver-metallic stoving lacquer based on polyester/
cellulose acetobutyrate/melamine resin. After exposure to the air at room temperature for one hour, the specimens are stoved for 30 minutes at 135C. The Layer thickness of the surface lacquer is about 40 /um.
The discoloration occurring on stovlng is me~sured according to DIN 6174 as shade clifference ~ E.
There are compared in each case the free hydroxy-benzotriazoles and the 0-acyl compounds thereof.
Table 4 Li~ht stabiliser E
none 0 7 _ 2% of compound No. 8 1.0 2% of comparison B 12.8 2% of compound No. 6 0.7 2% of comparison C 4.4 comparison B = 2-[2-hydroxy-3,5-di(l~l-dimethylbenzyl)-phenyl]-benzotriazole comparison,C = 2 ~2-hydroxy-3,5-di(tert-pentyl) phenyl]-~ ~ benzotriazoLe.
: :
' , ,.
, .
~ ~j3 ~5 Example 5 - Discoloration on weatherin~
The clear lacquer described in Example 1 is applied in a dry-film thickness of 40,um to metal sheet primed white. The specimens are stoved at 130C for 30 minutes and then weathered in a Florida apparatus for 3 months.
The degree of whiteness according to DIN 6174 is measured before and after weathering, and from the result is determined in each case the shade difference ~\E. The results are summarised in Table 5.
Table 5 Light stabiliser ~ E
none 3.2 2% of compound No. 6 1.0 2% of compound No. 13 0.8 2% of compound No. 20 o.6 2% of compound No. 46 1.0 2% of compound No. 52 1.2 xample 6 - Combination with a catalyst which can be cleaved_~y W
A acid-curable acrylic resin/melamine resin clear lacquer is prepared from:
57.3 parts o Acryloid ~ AT 410 (acrylic resin, Rohm and Haas Corp., USA) (75% solids content), 18.0 parts of Cymel ~ 301 (melamine resin, Amer. Cyanamid), 10.0 parts of butylacetate, 1.8 parts of cellulose acetobutyrate CAB 551 (Eastman Chem. Corp.), 2.6 parts of a flow-control agent (Modaflow ~ , Monsanto Corp.) and 10.5 parts of butanol.
The solids content of the lacquer is 653/3. The lacquer 35.
is knife-coated in a dry-film thickness of 40 ~m onto glass plates. The specimens are irradiated for 10 seconds with a 160 W W -lamp, and then stoved at 120C for 30 minutes.
There is used as a curing catalyst tha~ can be activated by W light 1% of benzoin-p-toluenesulfonate, which cleaves off p-toluenesulfonic acid on exposure to UV light. A blocked acid catalyst of this type has the advantage that it eEfects no curing in darkness. It has the disadvantage that in the presence of W-absorber light stabilisers the curing of the lacquer is incomplete. When however there is used as light stabilisers the 0-acylated benzotriazoles according to the invention, the activity of the curing catalyst is not hindered, as is shown by the ~ollowing Table 6. The curing o~ the lacquer is assessed in these tests by measurement of the pendulum hardness according to DIN 53157. The specimens are subsequently weathered in the Xenon Weatherometer, and the percentage gloss retention is thus determined.
Table 6 Light stabiliserGloss retention in % Pendulum after weathering of hardness 1000 h 2000 h 3000 h (sec) ~ . ~
none 83 S - 204 *
1% of comparison C 91 82 4 78 1% of compound No. 2 70 56 2 154 lZ of compound No. 5 75 77 6 lSS
1% of compound No. S
+ 1% of HALS*'~ 102 63 23 122 1% of compound No. 6 98 78 S 158 , ...
1~3'3'jS
) comparison C = 2-~-hydroxy-3,5-di-tert-pentyl-pheny~-benzotriazole (Tinuvin 328) **) HALS = 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4,5]decanedione-2,4 (Tinuvin ~ 440) : It is seen from the above that the free benzotriazole (comparison C) does provide good protection against light but greatly reduces the curing of the lacquer. With the light stabilisers according to the invention there is however obtained both a good protection against light ~ :and satisfactory curing. The level of protection against : : : light can be increased by the addition o a light stab:iliser : ~ of the sterically hindered amine type (HALS)~
,~:~: : :
' ~ :
., :
.
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS.
1. Coating material containing, as a crypto light stabiliser, a compound of the formula I or II
I
II
wherein x is 1 R1 is an acyl group of the formula -CO-R5, a sulfonyl group of the formula -SO2-R6, a phosphoryl group of the formula -P(Or(R14)(R15), R2 is C1-C12-alkyl, C5-C12-cycloalkyl, phenyl, C7-C9-phenylalkyl, C3-C5-alkenyl or halogen, R3 in the formula I is C1-C12-alkyl, C5-C12-cycloalkyl, phenyl, C7-C9-phenylalkyl, halogen or a group of the formula -(CH2)n-COOR9 or -(CH2)n-CO-N(R10)(R11), and in the formula II is a divalent radical of the formula:
-(CH2)n-CO-O-(CH2)q-O-CO-(CH2)n-, -(CH2)n-CO-O-(CH2CH2O)p-CO-(CH2)n-, -(CH2)n-CO-NH-R12-NH-CO-(CH2)n- or -(CH2)n-CO-O-CH2-,?-CH2-O-(CH2)q-O-CH2-,?CH2-O-CO-(CH2)n-, R4 is hydrogen, halogen, C1-C8-alkyl, C7-C9-phenylalkyl, C1-C8-alkoxy or C2-C8-alkoxycarbonyl, R5 is C1-C18-alkyl, C2-C18-alkenyl, -CH2-CO-CH3, phenyl, phenyl substituted by C1-C12-alkyl, C1-C4-alkoxy or benzoyl, or is C7-C12-arylalkyl or C1-C12-alkoxy, R6 is C1-C12-alkyl, C6-C10-aryl or C7-C18-alkylaryl, R9 is hydrogen, C1-C12-alkyl or a group of the formula -(CH2CH2O)p-R1, R10 and R11 independently of one another are hydrogen, C1-C12-alkyl, which can be interrupted by O or N, C5-C12-cyclo-alkyl, C7-C9-phenylalkyl, C3-C5-alkenyl, phenyl or a 2,2,6,6-tetramethyl-4-piperidinyl radical, or R10 and R11 together are C4-C6-alkylene, -oxaalkylene or -azaalkylene, R12 is C1-C12-alkylene, which can be interrupted by 1-3 O atoms, R13 is C1-C12-alkyl or C6-C10-aryl, R14 and R15 independently of one another are each C1-C12-alkoxy, phenoxy, C1-C12-alkyl, cyclohexyl, benzyl, phenyl or tolyl, n is 1 or 2, p is a number from 1 to 10, q is a number from 2 to 12, and r is 0 or 1.
I
II
wherein x is 1 R1 is an acyl group of the formula -CO-R5, a sulfonyl group of the formula -SO2-R6, a phosphoryl group of the formula -P(Or(R14)(R15), R2 is C1-C12-alkyl, C5-C12-cycloalkyl, phenyl, C7-C9-phenylalkyl, C3-C5-alkenyl or halogen, R3 in the formula I is C1-C12-alkyl, C5-C12-cycloalkyl, phenyl, C7-C9-phenylalkyl, halogen or a group of the formula -(CH2)n-COOR9 or -(CH2)n-CO-N(R10)(R11), and in the formula II is a divalent radical of the formula:
-(CH2)n-CO-O-(CH2)q-O-CO-(CH2)n-, -(CH2)n-CO-O-(CH2CH2O)p-CO-(CH2)n-, -(CH2)n-CO-NH-R12-NH-CO-(CH2)n- or -(CH2)n-CO-O-CH2-,?-CH2-O-(CH2)q-O-CH2-,?CH2-O-CO-(CH2)n-, R4 is hydrogen, halogen, C1-C8-alkyl, C7-C9-phenylalkyl, C1-C8-alkoxy or C2-C8-alkoxycarbonyl, R5 is C1-C18-alkyl, C2-C18-alkenyl, -CH2-CO-CH3, phenyl, phenyl substituted by C1-C12-alkyl, C1-C4-alkoxy or benzoyl, or is C7-C12-arylalkyl or C1-C12-alkoxy, R6 is C1-C12-alkyl, C6-C10-aryl or C7-C18-alkylaryl, R9 is hydrogen, C1-C12-alkyl or a group of the formula -(CH2CH2O)p-R1, R10 and R11 independently of one another are hydrogen, C1-C12-alkyl, which can be interrupted by O or N, C5-C12-cyclo-alkyl, C7-C9-phenylalkyl, C3-C5-alkenyl, phenyl or a 2,2,6,6-tetramethyl-4-piperidinyl radical, or R10 and R11 together are C4-C6-alkylene, -oxaalkylene or -azaalkylene, R12 is C1-C12-alkylene, which can be interrupted by 1-3 O atoms, R13 is C1-C12-alkyl or C6-C10-aryl, R14 and R15 independently of one another are each C1-C12-alkoxy, phenoxy, C1-C12-alkyl, cyclohexyl, benzyl, phenyl or tolyl, n is 1 or 2, p is a number from 1 to 10, q is a number from 2 to 12, and r is 0 or 1.
2. Coating material according to claim 1, which contains a compound of the formula I wherein x = 1, R1 is a group of the formula -CO-R5, -SO2-R6 or -P(O) (R14)(R15), R2 is C1-C12-alkyl, cyclohexyl or C7-C9-phenylalkyl, R3 is C1-C12-alkyl, cyclohexyl, C7-C9-phenylalkyl or a group -CH2CH2COOR9, R4 is hydrogen, methyl or chlorine, R5 is C1-C12-alkyl, C2-C4-alkenyl, phenyl, benzyl or naphthylmethyl, R6 is methyl, phenyl or C7-C18-alkylphenyl, R9 is C1-C12-alkyl, and R14 and R15 independently of one another are each C1-C4-alkoxy, methyl or phenyl.
3. Coating material according to claim 2, wherein R1 is a group of the formula -CO-R5 or -SO2-R6, and R5 and R6 have the meanings defined in claim 2.
4. Coating material according to claim 3, wherein R2 is C1-C8-alkyl or .alpha.-dimethylbenzyl, R3 is C1-C8-alkyl, .alpha.-dimethylbenzyl or a group -CH2CH2COOR9, R4 is hydrogen or chlorine, and R1 and R9 have the meanings defined in claim 3.
5. Coating material according to claim 1, which contains a compound of the formula I wherein x = 1, R1 is a group -CO-R5 or -SO2-R6, R2 is C1-C8-alkyl or .alpha.-dimethylbenzyl, R3 is C1-C8-alkyl, .alpha.-dimethylbenzyl or -CH2CH2COOR9, R4 is hydrogen or chlorine, R5 is C1-C12-alkyl, C2-C4-alkenyl, phenyl, benzyl or naphthylmethyl, R6 is methyl, phenyl or C7-C18-alkylphenyl, and R9 is C1-C12-alkyl.
6 Coating material according to claim 1, which contains a compound of the formula II wherein R1 is a group of the formula -CO-R5 or -SO2-R6, R2 is C1-C8-alkyl or .alpha.-dimethyl-benzyl, R3 is a group of the formula -CH2CH2COO-(CH2)q--OCOCH2CH2- or -CH2CH2CONH-R12-NHCOCH2CH2-, R4 is hydrogen or chlorine, R5 is C1-C12-alkyl, C2-C4-alkenyl, phenyl, benzyl or naphthylmethyl, R6 is methyl, phenyl or C7-C18-alkylphenyl, R12 is C2-C8-alkylene, and q is a number from 2 to 8.
7. Coating material according to claim 1, which contains a binder selected from the series comprising: alkyd resins, acrylic resins, epoxide resins, melamine resins, urea resins, polyurethanes, polyesters and phenolic resins, and mixtures thereof with one another.
8. Coating material according to claim 1, which contains as binder an oxidatively drying resin or resin mixture, and as curing catalyst an organic metal compound.
9. Coating material according to claim 1, which during its application comes into contact with copper or with a copper alloy.
10. A compound of the formula I or II
I
II
wherein x is 1 R1 is an acyl group of the formula -CO-R5, a sulfonyl group of the formula -SO2-R6, a phosphoryl group of the formula -P(O)r(R14)(R15), R2 is C1-C12-alkyl, C5-C12-cycloalkyl, phenyl, C7-C9-phenylalkyl, C3-C5-alkenyl or halogen, R3 in the formula I is a group of the formula -(CH2)n-COOR9 or -(CH2)n-CO-N(R1O)(R11), and in the formula II is a divalent group of the formula:
-(CH2)n-CO-O-(CH2)q-O-CO-(CH2)n-, -(CH2)n-CO-O-(CH2CH2O)p-CO-(CH2)n-, -(CH2)n-CO-NH-R12-NH-CO-(CH2)n- or -(CH2)n-CO-O-CH2-?-CH2-O-(CH2)q-O-CH2-,?-CH2-O-CO-(CH2)n-, R4 is hydrogen, halogen, C1-C8-alkyl, C7-C9-phenylalkyl, C1-C8-alkoxy or C2-C8-alkoxycarbonyl, R5 is C1-C18-alkyl, C2-C18-alkenyl, -CH2-CO-CH3, phenyl, phenyl substituted by C1-C12-alkyl, C1-C4-alkoxy or benzoyl, or is C7-C12-arylalkyl or C1-C12-alkoxy, R6 is C1-C12-alkyl, C6-C10-aryl or C7-C18-alkylaryl, R9 is hydrogen, C1-C12-alkyl or a group of the formula -(CH2CH2O)p-R1, R10 and R11 independently of one another are hydrogen, C1-C12-alkyl, which can be interrupted by O or N, C5-C12-cyclo-alkyl, C7-C9-phenylalkyl, C3-C5-alkenyl, phenyl or a 2,2,6,6-tetramethyl-4-piperidinyl radical, or R10 and R11 together are C4-C6-alkylene, -oxaalkylene or -azaalkylene, R12 is C1-C12-alkylene, which can be interrupted by 1-3 O atoms, R13 is C1-C12-alkyl or C6-C10-aryl, R14 and R15 independently of one another are each C1-C12-alkoxy, phenoxy, C1-C12-alkyl, cyclohexyl, benzyl, phenyl or tolyl, n is 1 or 2, p is a number from 1 to 10, q is a number from 2 to 12, and r is 0 or 1.
I
II
wherein x is 1 R1 is an acyl group of the formula -CO-R5, a sulfonyl group of the formula -SO2-R6, a phosphoryl group of the formula -P(O)r(R14)(R15), R2 is C1-C12-alkyl, C5-C12-cycloalkyl, phenyl, C7-C9-phenylalkyl, C3-C5-alkenyl or halogen, R3 in the formula I is a group of the formula -(CH2)n-COOR9 or -(CH2)n-CO-N(R1O)(R11), and in the formula II is a divalent group of the formula:
-(CH2)n-CO-O-(CH2)q-O-CO-(CH2)n-, -(CH2)n-CO-O-(CH2CH2O)p-CO-(CH2)n-, -(CH2)n-CO-NH-R12-NH-CO-(CH2)n- or -(CH2)n-CO-O-CH2-?-CH2-O-(CH2)q-O-CH2-,?-CH2-O-CO-(CH2)n-, R4 is hydrogen, halogen, C1-C8-alkyl, C7-C9-phenylalkyl, C1-C8-alkoxy or C2-C8-alkoxycarbonyl, R5 is C1-C18-alkyl, C2-C18-alkenyl, -CH2-CO-CH3, phenyl, phenyl substituted by C1-C12-alkyl, C1-C4-alkoxy or benzoyl, or is C7-C12-arylalkyl or C1-C12-alkoxy, R6 is C1-C12-alkyl, C6-C10-aryl or C7-C18-alkylaryl, R9 is hydrogen, C1-C12-alkyl or a group of the formula -(CH2CH2O)p-R1, R10 and R11 independently of one another are hydrogen, C1-C12-alkyl, which can be interrupted by O or N, C5-C12-cyclo-alkyl, C7-C9-phenylalkyl, C3-C5-alkenyl, phenyl or a 2,2,6,6-tetramethyl-4-piperidinyl radical, or R10 and R11 together are C4-C6-alkylene, -oxaalkylene or -azaalkylene, R12 is C1-C12-alkylene, which can be interrupted by 1-3 O atoms, R13 is C1-C12-alkyl or C6-C10-aryl, R14 and R15 independently of one another are each C1-C12-alkoxy, phenoxy, C1-C12-alkyl, cyclohexyl, benzyl, phenyl or tolyl, n is 1 or 2, p is a number from 1 to 10, q is a number from 2 to 12, and r is 0 or 1.
11. A compound of the formula I according to claim 10, wherein x = 1 or 2, R1 when x = 1 is a group of the formula -CO-R5 or -SO2-R6, and when x = 2 is a group -CO-R7-CO-, R2 is C1-C12-alkyl, cyclohexyl or C7-C9-phenylalkyl, R3 is a group -CH2CH2COOR9, R4 is hydrogen, methyl or chlorine, R5 is C1-C12-alkyl, C2-C4-alkenyl, phenyl, benzyl or naphthylmethyl, R6 is methyl, phenyl or C7-C15-alkylphenyl, and R9 is C1-C12-alkyl.
12. A compound of the formula I according to claim 11, wherein x = 1, R1 is a group -CO-R5 or -SO2-R6, R2 is C1-C8-alkyl or .alpha.-dimethylbenzyl, R4 is hydrogen or chlorine, and R3, R5 and R6 have the meanings defined in claim 11.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH522084 | 1984-11-01 | ||
| CH5220/84-6 | 1985-02-01 | ||
| CH45385 | 1985-02-01 | ||
| CH453/85-0 | 1985-02-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1263955A true CA1263955A (en) | 1989-12-19 |
Family
ID=25684622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000494241A Expired CA1263955A (en) | 1984-11-01 | 1985-10-30 | Coating materials stabilised against the action of light |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US4775707A (en) |
| EP (1) | EP0180548B1 (en) |
| JP (1) | JP2597830B2 (en) |
| CA (1) | CA1263955A (en) |
| DE (1) | DE3571251D1 (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3571251D1 (en) * | 1984-11-01 | 1989-08-03 | Ciba Geigy Ag | Coatings stabilized against the action of light |
| US4926190A (en) * | 1987-02-18 | 1990-05-15 | Ciba-Geigy Corporation | Ink jet recording process using certain benzotriazole derivatives as light stabilizers |
| US5162405A (en) * | 1987-12-24 | 1992-11-10 | Elf Atochem North America, Inc. | Single-functional and mixtures of multi-functional oligomeric performance additive compositions and their uses |
| DE3888952D1 (en) * | 1987-12-28 | 1994-05-11 | Ciba Geigy | New 2- (2-hydroxyphenyl) benzotriazole derivatives. |
| EP0453396B1 (en) * | 1990-03-30 | 1995-12-13 | Ciba SC Holding AG | Paint compositions |
| US5086097A (en) * | 1991-01-07 | 1992-02-04 | Mobay Corporation | Ultraviolet stabilizer for polycarbonate compositions |
| EP0711804A3 (en) | 1994-11-14 | 1999-09-22 | Ciba SC Holding AG | Latent light stabilizers |
| US6218463B1 (en) * | 1998-04-20 | 2001-04-17 | Johnson & Johnson Vision Care, Inc. | Ocular devices manufactured with free radical-polymerizable latent ultra-violet absorbers |
| EP1089986B1 (en) | 1998-06-22 | 2005-03-30 | Ciba SC Holding AG | Poly-trisaryl-1,3,5-triazine carbamate ultraviolet light absorbers |
| US6297377B1 (en) | 1998-06-22 | 2001-10-02 | Cytec Technology Corporation | Benzocycle-substituted triazine and pyrimidine ultraviolet light absorbers |
| US6239276B1 (en) | 1998-06-22 | 2001-05-29 | Cytec Technology Corporation | Non-yellowing para-tertiary-alkyl phenyl substituted triazine and pyrimidine ultraviolet light absorbers |
| JP2002518486A (en) | 1998-06-22 | 2002-06-25 | サイテク・テクノロジー・コーポレーシヨン | Trisaryl-1,3,5-triazine UV light absorber shifted to red side |
| TWI259182B (en) | 1998-11-17 | 2006-08-01 | Cytec Tech Corp | Process for preparing triazines using a combination of Lewis acids with reaction promoters |
| US6867250B1 (en) | 2000-10-30 | 2005-03-15 | Cytec Technology Corp. | Non-yellowing ortho-dialkyl aryl substituted triazine ultraviolet light absorbers |
| US20100074949A1 (en) | 2008-08-13 | 2010-03-25 | William Rowe | Pharmaceutical composition and administration thereof |
| JP2002264500A (en) | 2001-03-14 | 2002-09-18 | Fuji Photo Film Co Ltd | Heat sensitive recording material |
| US20030141491A1 (en) * | 2001-11-05 | 2003-07-31 | Fuji Photo Film Co., Ltd. | Heat-sensitive recording material |
| US6855269B2 (en) * | 2001-11-09 | 2005-02-15 | Cytec Technology Corp. | Phenyl ether-substituted hydroxyphenyl triazine ultraviolet light absorbers |
| ATE449948T1 (en) * | 2003-12-29 | 2009-12-15 | Ruag Land Systems | PROTECTIVE LAYER AGAINST SHAPED LOADS |
| LT2489659T (en) | 2004-06-24 | 2018-03-26 | Vertex Pharmaceuticals Incorporated | Modulators of ATP-binding cassette transporters |
| RS60205B1 (en) | 2005-12-28 | 2020-06-30 | Vertex Pharma | Pharmaceutical compositions of the amorphous form of n-[2,4-bis(1,1-dimethylethyl)-5-hydroxyphenyl]-1,4-dihydro-4-oxoquinoline-3-carboxamide |
| CN109966264A (en) | 2012-02-27 | 2019-07-05 | 沃泰克斯药物股份有限公司 | Pharmaceutical composition and its application |
| JP6312259B2 (en) * | 2012-07-31 | 2018-04-18 | 株式会社Adeka | Latent additive and composition containing the additive |
| WO2017007672A1 (en) | 2015-07-07 | 2017-01-12 | 3M Innovative Properties Company | Substituted benzotriazole phenols |
| CN114685710B (en) * | 2022-04-27 | 2024-01-09 | 西尼尔(山东)新材料科技有限公司 | Preparation method of furyl light stabilizer for PBS (phosphate buffer solution) |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH410968A (en) * | 1961-06-16 | 1966-04-15 | Geigy Ag J R | Process for the preparation of substituted 2- (2'-hydroxyphenyl) benzotriazole compounds |
| GB1158548A (en) * | 1965-07-26 | 1969-07-16 | Nitto Kasei Co Ltd | Stabilizing Synthetic Polymer against Light |
| JPS4530567Y1 (en) * | 1966-08-30 | 1970-11-24 | ||
| US3936418A (en) * | 1974-10-02 | 1976-02-03 | Eastman Kodak Company | Benzotriazole ortho-ester ultraviolet stabilizers and their use in organic compositions |
| US4041011A (en) * | 1974-10-02 | 1977-08-09 | Eastman Kodak Company | Benzotriazole ortho-ester ultraviolet stabilizers |
| US4061652A (en) * | 1975-10-28 | 1977-12-06 | General Electric Company | Urethanes of hydroxybenzotriazoles |
| US4344830A (en) * | 1976-02-23 | 1982-08-17 | General Electric Company | UV Curable resins and sulfonate esters of benzotriazoles used in such resins |
| JPS53110528A (en) * | 1977-03-08 | 1978-09-27 | Konishiroku Photo Ind Co Ltd | Color photographic material with fading resistance improved |
| WO1982002397A1 (en) * | 1980-12-31 | 1982-07-22 | Pont Du | Thermosetting acrylic enamel stabilized against weathering by addition of ultraviolet light stabilizer |
| JPS598751A (en) * | 1982-07-07 | 1984-01-18 | Mitsubishi Gas Chem Co Inc | Stabilized polyphenylene ether resin composition |
| JPS6071663A (en) * | 1983-09-28 | 1985-04-23 | Toray Ind Inc | Polyphenylene sulfide film |
| DE3571251D1 (en) * | 1984-11-01 | 1989-08-03 | Ciba Geigy Ag | Coatings stabilized against the action of light |
-
1985
- 1985-10-28 DE DE8585810487T patent/DE3571251D1/en not_active Expired
- 1985-10-28 EP EP85810487A patent/EP0180548B1/en not_active Expired
- 1985-10-30 CA CA000494241A patent/CA1263955A/en not_active Expired
- 1985-11-01 JP JP60246089A patent/JP2597830B2/en not_active Expired - Lifetime
-
1987
- 1987-06-22 US US07/065,655 patent/US4775707A/en not_active Expired - Lifetime
-
1989
- 1989-10-24 US US07/427,919 patent/US5030731A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US5030731A (en) | 1991-07-09 |
| DE3571251D1 (en) | 1989-08-03 |
| EP0180548A3 (en) | 1987-02-04 |
| JPS61109778A (en) | 1986-05-28 |
| JP2597830B2 (en) | 1997-04-09 |
| US4775707A (en) | 1988-10-04 |
| EP0180548B1 (en) | 1989-06-28 |
| EP0180548A2 (en) | 1986-05-07 |
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